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EP3182178A1 - Optisches element - Google Patents

Optisches element Download PDF

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Publication number
EP3182178A1
EP3182178A1 EP15822124.2A EP15822124A EP3182178A1 EP 3182178 A1 EP3182178 A1 EP 3182178A1 EP 15822124 A EP15822124 A EP 15822124A EP 3182178 A1 EP3182178 A1 EP 3182178A1
Authority
EP
European Patent Office
Prior art keywords
optical element
concave protrusions
steps
protrusions
concave
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP15822124.2A
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English (en)
French (fr)
Other versions
EP3182178A4 (de
EP3182178B1 (de
Inventor
Koki Hongo
Kei Shinotsuka
Kotaro DAI
Keiichi Kajita
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Oji Holdings Corp
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Oji Holdings Corp
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Publication date
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Publication of EP3182178A1 publication Critical patent/EP3182178A1/de
Publication of EP3182178A4 publication Critical patent/EP3182178A4/de
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/111—Anti-reflection coatings using layers comprising organic materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/118—Anti-reflection coatings having sub-optical wavelength surface structures designed to provide an enhanced transmittance, e.g. moth-eye structures
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
    • G02B27/0018—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00 with means for preventing ghost images
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • G02B5/0205—Diffusing elements; Afocal elements characterised by the diffusing properties
    • G02B5/021—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures
    • G02B5/0231—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures the surface having microprismatic or micropyramidal shape

Definitions

  • the present invention relates to an optical element.
  • a film-like anti-reflection structure for improving visibility is provided on the surface of a display, for example, a computer or the like.
  • a method for preventing reflection by closely disposing a plurality of fine convex protrusions on the surface of a transparent substrate (transparent film) has been proposed as this anti-reflection structure.
  • the so-called "moth-eye structure" principle is applied in this method. Moth-eye structures seek to prevent reflection by continuously varying the refractive index with respect to incident light in a thickness direction of the substrate, thereby sudden fluctuations in refractive index at the interfaces are eliminated and anti-reflectivity is obtained.
  • anti-reflection structures are not limited to fine convex protrusions and may also be fine concave protrusions. It is preferable that a ratio of height or depth of the fine convex protrusions or concave protrusions to a width of the structure (hereinafter referred to as the "aspect ratio") be great. This is because when the aspect ratio is great, the refraction index changes will be gradual and high antireflective performance can be obtained. On the other hand, with larger aspect ratios, stability of the anti-reflection structure provided with the convexity or concave protrusion structure is lost.
  • Patent Literature 1 describes improving the antireflective performance of an optical element by providing two or more steps in convex protrusions or concave protrusions. If two or more steps are provided in the convex protrusions or concave protrusions, discontinuous interfaces will occur in the interfaces where the refractive index of the moth-eye structure continuously varies. These discontinuous interfaces reflect a portion of the incident light. Patent Literature 1 suggests that the reflected light can be reduced by causing the light reflected at the discontinuous interfaces to interfere with each other.
  • Patent Literature 1 Japanese Unexamined Patent Application Publication No. 2010-79200A
  • Patent Literature 1 has not provided sufficient antireflective performance.
  • the frequency at which reflected light interferes must be increased and, to do so, more steps must be formed in the convex protrusions or the concave protrusions.
  • fabricating convex protrusions or concave protrusions with many steps requires a complex process and, consequently, fabrication has been difficult.
  • an object of the present invention is to provide an optical element with high antireflective performance and which can be easily manufactured.
  • the present inventors focused on the width of steps and the position of steps of concave protrusions formed in an anti-reflection layer.
  • the present inventors discovered that it is preferable that the width and the position of the steps of the concave protrusions be provided in predetermined ranges.
  • the present invention includes the following inventions:
  • the optical element of the present invention includes, on a substrate, an anti-reflection layer in which small concave protrusions are formed, and the concave protrusions include steps of a predetermined width and at predetermined positions.
  • the concave protrusions include steps of a predetermined width and at predetermined positions.
  • FIG. 1 is a cross-sectional view schematically illustrating an optical element of the present invention.
  • FIG. 2 is a perspective view schematically illustrating the optical element of the present invention.
  • FIG. 3 is a plan view schematically illustrating the optical element of the present invention.
  • An optical element 10 is provided with, on a substrate 1, an anti-reflection layer 2 in which a plurality of small concave protrusions c1 to cn, which have a modal pitch P less than or equal to a wavelength of light in an environment where the optical element is to be used, are formed.
  • the optical element 10 may include a flat portion f between the concave protrusions c1 to cn.
  • t1 to tn are central points of the concave protrusions c1 to cn.
  • the center of gravity of each contour line (point determined by an X-coordinate and a Y-coordinate) is found by drawing a plurality of contour lines parallel to a reference plane for each of the concave protrusions at 20 nm intervals, on the basis of the result of measurements by an AFM (atomic force microscope).
  • An average position of the centers of gravity (place determined by the average of the X-coordinates and the average of the Y-coordinates) is the central point of the concave protrusion.
  • m1 to mn are midpoints between adjacent central points, found using the AFM.
  • the flat portion f is a region where, on the basis of the results of measurements by AFM, a slope of a straight line connecting a positional coordinate at the midpoint in the region with a positional coordinate of any point in the region, with respect to a reference plane of the AFM, is ⁇ 10° or less.
  • the reference plane is a plane that is parallel with a reference plane in the measurement region and is a plane that passes through a reference point (described later).
  • the modal pitch P is a distance between adjacent concave protrusions and, specifically, can be found as follows.
  • an AFM image is obtained for a square region of which one side thereof is from 30 to 40 times the modal pitch P.
  • the modal pitch P is about 300 nm
  • an image of a 9 ⁇ m ⁇ 9 ⁇ m to 12 ⁇ m ⁇ 12 ⁇ m region is obtained.
  • this image is subjected to waveform separation by Fourier transformation to obtain a fast Fourier transform image (FFT image).
  • FFT image fast Fourier transform image
  • the reciprocal of the distance thus determined is the modal pitch P in that region.
  • This process is performed in the same manner for not less than a total of 25 randomly selected regions of the same area, and the modal pitch in each region is determined.
  • the average of the modal pitches P 1 to P 25 of the not less than 25 regions obtained in this manner is the modal pitch P. Note that, at this time, it is preferable that regions that are at least 1 mm apart are selected, and it is more preferable that regions that are from 5 mm to 1 cm apart from each other are selected.
  • the concave protrusions c1 to cn may be divided into a plurality of areas C 1 to C n .
  • the areas C 1 to C n are regions continuously arranged in a positional relationship in which the central point of seven adjacent concave protrusions is an intersection point of diagonal lines of six vertices of a regular hexagon. Note that in FIG. 3 , for convenience, the position of the central point of each concave protrusion is indicated by a circle u centered on that central point.
  • the positional relationship a positional relationship so that the central points of the seven adjacent concave protrusions are to become six vertices and intersection point of diagonal lines of a regular hexagon refers to a relationship that satisfies the following conditions.
  • a line segment L1 of a length equal to the modal pitch P is drawn from one central point t1 toward an adjacent central point t2.
  • line segments L2 to L6 of lengths equal to the modal pitch P are drawn from the central point t1 in directions 60°, 120°, 180°, 240°, and 300° with respect to the line segment L1.
  • the central points of these seven convex protrusions are in a positional relationship where the central point t1 is an intersection point of the diagonal lines of six vertices of a regular hexagon.
  • a modal area Q of the areas C 1 to C n (the mode of the area size) is preferably in the following range.
  • the modal area Q within a 10 ⁇ m ⁇ 10 ⁇ m AFM image measurement range is preferably from 0.026 ⁇ m 2 to 6.5 ⁇ m 2 .
  • the modal area Q within a 10 ⁇ m ⁇ 10 ⁇ m AFM image measurement range is preferably from 0.65 ⁇ m 2 to 26 ⁇ m 2 .
  • the modal area Q within a 50 ⁇ m ⁇ 50 ⁇ m AFM image measurement range is preferably from 2.6 ⁇ m 2 to 650 ⁇ m 2 .
  • the modal area Q is within the preferred range, it is easier to prevent the problem of viewing angle dependence on antireflective performance.
  • areas, shapes, and crystal orientations of the areas C 1 to C n are random.
  • the degree of randomness of the area preferably satisfies the following conditions.
  • the standard deviation of ⁇ ab within a 10 ⁇ m ⁇ 10 ⁇ m AFM image measurement range is preferably not less than 0.08 ⁇ m 2 .
  • the standard deviation of ⁇ ab within a 10 ⁇ m ⁇ 10 ⁇ m AFM image measurement range is preferably not less than 1.95 ⁇ m 2 .
  • the standard deviation of ⁇ ab within a 50 ⁇ m ⁇ 50 ⁇ m AFM image measurement range is preferably not less than 8.58 ⁇ m 2 .
  • the standard deviation of the ratio of a to b (a / b) in Formula (7) above is preferably not less than 0.1.
  • the randomness of the crystal orientation of the areas C 1 to C n preferably satisfies the following conditions.
  • a straight line K0 is drawn connecting the central points of any two adjacent concave protrusions in any area (I). Then, one area (II) adjacent to the area (I) is chosen, and six straight lines K1 to K6 are drawn connecting any concave protrusion in the area (II) and the central points of six concave protrusions adjacent to that concave protrusion.
  • the crystal orientations of the area (I) and the area (II) are defined as being different when all of the lines K1 to K6 are at an angle of not less than 3 degrees with respect to the straight line K0.
  • the areas adjacent to the area (I) there are preferably not less than two areas having a different crystal orientation than the area (I), and more preferably not less than three such areas, and even more preferably not less than five such areas.
  • the crystal orientations of the concave protrusions c1 to cn are ordered within the areas C 1 to C n , but, macroscopically, the concave protrusions c1 to cn are random polycrystalline structures.
  • the macroscopic randomness of the crystal orientations can be evaluated using a ratio of the maximum value to the minimum value of the Fast Fourier Transform (FFT) fundamental wave.
  • FFT Fast Fourier Transform
  • the ratio of the maximum value to the minimum value of the FFT fundamental wave is found by acquiring an AFM image, finding the two-dimensional Fourier Transform image of the AFM image, drawing a circumference distanced from an origin point the number of fundamental waves, extracting the point of greatest amplitude and the point of least amplitude on this circumference, and taking the ratio of these amplitudes.
  • the method for acquiring the AFM image is the same as the method for acquiring the AFM image when finding the modal pitch P.
  • the crystal orientations of the concave protrusions are ordered and, when the concave protrusions are viewed as two-dimensional crystals, it can be said that the structure is highly monocrystalline.
  • the crystal orientations of the concave protrusions are random and, when the concave protrusions are viewed as two-dimensional crystals, it can be said that the structure is polycrystalline.
  • the reflected light that has reflected at the step surfaces does not reflect in a specific in-plane direction, but instead reflects evenly.
  • in-plane reflection intensity does not change depending on the viewing angle. In other words, antireflective performance with low dependence on the viewing angle can be obtained.
  • 80% or more of the concave protrusions c1 to cn include one or more steps, and satisfy the following conditions.
  • d is a diameter of the concave protrusions
  • h is a depth of the concave protrusions
  • w s is a total width of the steps in any cut surface
  • z s is an average depth of the steps.
  • width and the depth of the steps are within the ranges described above, higher antireflective performance will be displayed compared to a stepless optical element.
  • width and the depth of the steps are within the ranges described above, high antireflective performance can be obtained even with three or fewer steps, and a desired optical element can be easily fabricated.
  • the proportion of concave protrusions that include steps is determined as follows.
  • a cross-section along a line having a length of 5 ⁇ m in any direction and at any position such as that illustrated in FIG. 1 is obtained from an AFM image.
  • the cross-section such as that illustrated in FIG. 1 may be obtained as a photomicrograph that was acquired by observing, using a microscope, a cross-section of a cut sample taken from the optical element.
  • the concave protrusion surface be covered or filled with a material capable of enduring the cutting, and then the optical element be cut.
  • the cross-section measured using an AFM image is given priority. This is because with the cross-section measured using an AFM image, it is easier to obtain a measurement surface of the cut surface that passes through the deepest portion of the concave protrusions, and it is easier to confirm the relationship between the width and the depth of the steps.
  • the cross-section is any plane perpendicular to the arrangement plane on which the concave protrusions are arranged. In cases where the concave protrusions are regularly arranged, it is preferable that the direction corresponding to the arrangement direction of the concave protrusions is used as the cutting direction in which the cross-section is obtained.
  • the shape (including the depth and step positions) of the concave protrusions may be confirmed by using the optical element as a mold and confirming the shape of convex protrusions on an transfer product obtained as a result of inverting/transferring the concave protrusions.
  • a cross-section of the transfer product may be measured using an AFM image, or a cut surface thereof may be directly observed using a microscope. From the perspective of obtaining a cut surface that passes through the apexes of the transfer product, it is preferable that the cut surface be measured using an AFM image.
  • any portion of the cross-section in which 30 to 40 or more concave protrusions are included is extracted, and the proportion of concave protrusions that include steps is calculated for the concave protrusions included in the extracted portion.
  • the diameter d can be found as a maximum diameter of the concave protrusions observed in a cross-section perpendicular to the arrangement plane of the concave protrusions.
  • the depth h can be obtained by calculating the difference in height between the deepest point and the highest portion (the portion farthest away from the deepest point in the cut surface; hereinafter referred to as the "reference point") of the concave protrusions observed in the cross-section perpendicular to the arrangement plane of the concave protrusions.
  • the steps, the width of the steps, and the depth of the steps are defined below.
  • the concave protrusions c1 to cn include fine unevennesses of a degree that can be ignored from the standpoint of the operations and effects.
  • the steps are set ignoring such fine unevennesses. Specifically, changes, with respect to a fitting curve, of 3% or less of the depth h of the concave protrusions c1 to cn are ignored.
  • FIGS. 4A to 4D are schematic drawings for explaining the definition of the steps.
  • inflection points in the broad sense, are defined.
  • an inflection point is a point where a curve on a plane changes from being convex upward to being convex downward or vice versa.
  • a reference point and a non-differentiable point are considered to be inflection points, in the broad sense of the term. Due to the relationship of the definition of the tangent to the inflection point (described later), for descriptive purposes, the curve is considered to have two inflection points at the non-differentiable point.
  • inflection points are, specifically, a point infinitely close to a point where the curve bends from the reference point side, and a point infinitely close to a point where the curve bends from the deepest point side.
  • the inflection points are numbered in order from that nearest to the reference point, and are defined as a first inflection point to an nth inflection point.
  • FIG. 4A The method for finding the inflection points in the broad sense is specifically illustrated in FIG. 4A .
  • the reference point is the first inflection point.
  • the points where the concavo-convex direction of the curve subsequently changes are the second inflection point and the third inflection point, in order from the point nearest to the reference point.
  • the point where the curve bends is the fourth inflection point and the fifth inflection point.
  • the points where the concavo-convex direction of the curve changes are the sixth inflection point and the seventh inflection point, in order from the point nearest to the reference point.
  • tangents are drawn at each of the inflection points. It is mathematically impossible to draw a tangent for the non-differentiable point.
  • the inflection points are set as the two points, namely a point infinitely close to the point where the curve bends from the reference point side, and a point infinitely close to the point where the curve bends from the deepest point side.
  • a tangent is drawn at each of these two points.
  • the tangents drawn at the two points specifically are a straight line having a slope immediately prior to the curve bending from the reference point side toward the deepest point side and a straight line having a slope immediately after the curve bends from the reference point side toward the deepest point side.
  • these two tangents can be drawn as illustrated in FIG. 4B .
  • FIG. 4B it is mathematically possible to draw tangents at the other inflection points.
  • points on the curve nearest to intersection points of the tangents drawn in the manner described above are defined as changing points (procedure c).
  • the two tangents described above are drawn, which results in the intersection point being the non-differentiable point. Accordingly, the non-differentiable point is one of the changing points.
  • the reference point is also a changing point because it is the origin point of the concave protrusion.
  • the changing points are numbered in order from the side near the reference point.
  • the changing points are connected by straight lines.
  • the changing point (seventh changing point) nearest to the deepest point does not have a subsequent changing point on the deepest point side to which the straight line can be connected.
  • a tangent is drawn at the changing point nearest to the deepest point.
  • the straight lines drawn in this manner are numbered in order from the reference point side.
  • a first straight line to a seventh straight line can be drawn.
  • this section of the nth straight line is defined as a "step" (procedure e).
  • the slope of the second straight line for example, is less than or equal to the absolute values of the slope of the first straight line and the slope of the third straight line and, therefore, is a step. The same is true for the fourth straight line and the sixth straight line.
  • the term "width of the steps” means a width of the steps as defined above, projected on a reference plane of the concave protrusion. That is, in FIG. 5 , the width of the first step is w 1 .
  • a total width of the steps is the total of the widths of each of the steps, and the total width w s of the steps is a value two-times w 1 +w 2 +w 3 .
  • the reason for multiplying by two is because the steps are formed equally in the circumferential direction of the concave protrusion, at the same depths. That is, in FIG.
  • depth of the steps means the depth from the reference plane, including the reference point, to a midpoint of the step. That is, for example, the depth of the first step as defined in FIG. 4D is z 1 .
  • An "average depth z s of the steps” means (z 1 +z 2 +z 3 )/3 in FIG. 5 . The reason why this value is not divided by 2 like with the width of the steps is because z s is an average.
  • concave protrusions c1 to cn include two or fewer steps, and satisfy the following conditions.
  • concave protrusions c1 to cn include one step, and satisfy the following conditions.
  • the highest antireflective performance can be obtained by the concave protrusions with one step, compared to those with a plurality of steps.
  • the optical element can be fabricated even more easily.
  • a modal depth of the concave protrusions c1 to cn is in a range of 45% to 55% of a median of a wavelength range of light in the environment where the optical element is to be used.
  • modal depth means the average depth of 30 to 40 or more concave protrusions in a cross-section such as that of FIG. 1 , obtained using AFM or a microscope.
  • the modal depth of the concave protrusions c1 to cn is excessively less than the median of the wavelength range of light in the environment where the optical element is to be used, continuous variations in the refractive index will become steep and, consequently, the antireflective performance will decline. If the modal depth of the concave protrusions c1 to cn is excessively greater than the median of the wavelength range of light in the environment where the optical element is to be used, the structural stability of the concave protrusions c1 to cn will decline and maintaining the structure will be difficult.
  • the modal depth of the concave protrusions c1 to cn is excessively greater than the median of the wavelength range of light in the environment where the optical element is to be used, transferring from the mold will be difficult.
  • the phrase "light in the environment where the optical element is to be used” refers to any one of ultraviolet light, visible light, and infrared light.
  • the “median of the wavelength range of light in the environment where the optical element is to be used” is, for example, 580 nm in a case where visible light, specifically light of 380 nm to 780 nm, is used.
  • the envelope of the concave protrusions c1 to cn is conical.
  • the continuous variation of the refractive index becomes gradual at the interface from the higher refractive index and steep at the interface from the lower refractive index and, as a result, higher antireflective performance can be obtained.
  • the optical element 10 does not include the flat portion f between the concave protrusions.
  • the optical element 10 has a protrusion in the region surrounded by the three concave protrusions forming the triangular lattice.
  • the protrusion is a portion protruding to the side opposite the substrate, beyond an average reference plane.
  • the term "average reference plane" means a plane that is parallel to the substrate, and that passes through an average point obtained by averaging the heights of the reference points (height in the vertical direction of the substrate) of 30 to 40 or more concave protrusions in a cross-section such as that of FIG. 1 , obtained using AFM or a microscope.
  • the optical element 10 has a protrusion in the region surrounded by the four concave protrusions.
  • a height of the protrusion with respect to the average reference plane is from 3 to 30% of the average depth of the concave protrusions.
  • the height of the protrusion with respect to the average reference plane is not less than 3% of the average depth of the concave protrusions.
  • anti-reflection effects can be enhanced further.
  • the height of the protrusion with respect to the average reference plane is not greater than 30% of the average depth of the concave protrusions, wear resistance of the optical element surface can be maintained.
  • the material of the anti-reflection layer 2 is not particularly limited.
  • the material may be an organic or inorganic material.
  • organic materials that may be used include generally used UV curable resins, thermoplastic resins, thermosetting resins, and the like.
  • examples of inorganic materials that can be used include Si, SiO 2 , SiON, Ni, spin on glass, and the like.
  • the substrate 1 is not particularly limited. Synthetic resins such as polyethylene terephthalate (PET), triacetyl cellulose (TAC), and the like; and inorganic films such as glass, semiconductors, and the like may be used. A flat layer made from the same material as the anti-reflection layer 2 may be used as the substrate 1.
  • the substrate 1 may be configured in, for example, a film form, a sheet form, a plate form, a block form, or the like.
  • the shape of the substrate 1 is not particularly limited and may be changed depending on the use/application thereof.
  • the optical element 10 having the concave protrusions c1 to cn described above can be used as an antireflective body to be applied to various types of displays (e.g. LCD displays, plasma displays, rear projectors, FEDs, OLEDs, and other FPDs) of a computer, a mobile phone, a digital camera or the like; and the surfaces of show windows and other glass windows, display frames, various display windows, optical lenses, solar batteries, optical materials from which road/traffic signs and signboards are made, and the like. Additionally, this optical element 10 can be used as an original plate of a nanoimprinting mold for manufacturing such an antireflective body.
  • displays e.g. LCD displays, plasma displays, rear projectors, FEDs, OLEDs, and other FPDs
  • this optical element 10 can be used as an original plate of a nanoimprinting mold for manufacturing such an antireflective body.
  • the optical element of the present invention can be obtained by transferring a mold having a predetermined shape an odd number of times.
  • the mold can be fabricated by using an etching mask in which a plurality of particles M are arranged two-dimensionally.
  • FIGS. 6A to 6D are drawings schematically illustrating the method for manufacturing the optical element of the present invention.
  • a a particle monolayer etching mask 12 made from a plurality of particles M, is formed on a mold substrate 11 ( FIG. 6A ).
  • a method employing, for example, the concept of the Langmuir-Blodgett method (LB method) can be used as the method for forming the a particle monolayer etching mask 12 on the mold substrate 11.
  • the a particle monolayer etching mask 12 can be formed on the mold substrate 11 via a method including a dripping step in which a dispersion having particles dispersed in a solvent is dripped on the surface of liquid in a water tank, a a particle monolayer formation step in which a a particle monolayer F made of particles is formed by volatilizing the solvent, and a transfer step in which the a particle monolayer F is transferred onto the substrate.
  • a dispersion is prepared by adding particles having hydrophobic surfaces to a hydrophobic organic solvent made of one or more types of solvents with high volatility such as chloroform, methanol, ethanol, methyl ethyl ketone, and the like.
  • a water tank (trough) V is prepared, and a liquid, namely water W for expanding the particles M on the surface thereof (hereinafter sometimes referred to as "lower-layer water”), is filled in the tank.
  • the dispersion is dripped onto the liquid surface of the lower-layer water (dripping step).
  • the solvent that is the dispersion medium volatilizes and the particles expand in a monolayer on the surface of the lower-layer water.
  • a two-dimensionally close-packed a particle monolayer F can be formed (a particle monolayer formation step).
  • the lower-layer water must be hydrophilic and, typically, water is used, as described above.
  • the hydrophobic particles and solvent By combining the hydrophobic particles and solvent with the hydrophilic lower-layer water, the self-assembly of the particles (described later) is promoted and a two-dimensionally close-packed a particle monolayer F is formed.
  • hydrophilic particles a hydrophilic solvent may also be used and, in this case, a hydrophobic liquid is selected as the lower-layer water.
  • the a particle monolayer F that has been formed on the liquid surface in the a particle monolayer formation step is transferred onto the etching subject, namely the mold substrate 11 in the single-layer state as-is (transfer step).
  • the mold substrate 11 may be flat, or a portion or entirety thereof may include a non-flat shape such as a curve, slope, step, or the like. It is possible to cover the substrate surface with the a particle monolayer F while maintaining the two-dimensionally close-packed state even if the mold substrate 11 is not flat.
  • the specific method for transferring the a particle monolayer F to the mold substrate 11 is not particularly limited, and examples thereof include a method wherein the hydrophobic mold substrate 11 is lowered from above and put in contact with the a particle monolayer F while being held substantially perpendicular to the a particle monolayer F, and the a particle monolayer F is transferred to the mold substrate 11 by the affinity force between the hydrophobic a particle monolayer F and the mold substrate 11; and a method wherein the mold substrate 11 is disposed in a substantially horizontal direction in the lower-layer water in a water tank prior to forming the a particle monolayer F, and after the a particle monolayer F is formed on the liquid surface, the a particle monolayer F is transferred to the mold substrate 11 by gradually lowering the liquid level.
  • the a particle monolayer F can be transferred to the mold substrate 11 without using special equipment by either of the above methods.
  • the so-called LB trough method is preferably employed because even if the a particle monolayer F has a larger area, it is easily transferred to the mold substrate 11 while maintaining its two-dimensionally close-packed state (refer to Journal of Materials and Chemistry, Vol. 11, 3333 (2001 ), Journal of Materials and Chemistry, Vol. 12, 3268 (2002 ), and the like).
  • the plurality of particles M are arranged in substantially a monolayer on one surface, namely a flat surface 11a, of the mold substrate 11. That is, a a particle monolayer F of the particles M is formed on the flat surface 11a.
  • the plurality of particles M are arranged in a monolayer on the mold substrate 11 such that divergence D (%) of the arrangement defined by Formula (8) below is not greater than 10%.
  • D % B ⁇ A ⁇ 100 / A
  • A is the average particle size of the particles M
  • B is the modal pitch between the particles M.
  • indicates the absolute value of the difference between A and B.
  • the divergence D is from 1.0 to 3.0%.
  • the average particle size A of the particles M is the average primary particle size of the particles M that constitute the a particle monolayer F, which can be determined by a commonly used method from the peak obtained by fitting the particle size distribution determined by particle dynamic light scattering to a Gaussian curve.
  • the pitch between the particles M is the distance in a sheet plane direction from vertex to vertex of two adjacent particles M
  • the modal pitch B is the average thereof. Note that when the particles M are spherical, the distance from vertex to vertex of adjacent particles M is equal to the distance from center to center of adjacent particles M.
  • the modal pitch B between the particles M is determined as follows.
  • an atomic force microscope image is obtained for a square region, parallel with the sheet plane, where one side thereof is from 30 to 40 times the modal pitch B between the particles M.
  • an image of a region from 9 ⁇ m ⁇ 9 ⁇ m to 12 ⁇ m ⁇ 12 ⁇ m is obtained.
  • this image is subjected to waveform separation by Fourier transformation, and a fast Fourier transform image (FFT image) is obtained.
  • FFT image fast Fourier transform image
  • This process is performed in the same manner for not less than a total of 25 randomly selected regions of the same area, and the modal pitches B 1 to B 25 in each region are determined.
  • the average of the modal pitches B 1 to B 25 of the not less than 25 regions obtained in this manner is the modal pitch B in Formula (8). Note that, at this time, it is preferable that regions that are at least 1 mm apart are selected, and it is more preferable that regions that are from 5 mm to 1 cm apart from each other are selected.
  • the divergence D of this arrangement is an indicator of the degree of close packing of the particles M. That is, a low divergence D of particle arrangement means that the degree of close packing is high, the gaps between particles are controlled, and the precision of their arrangement is high.
  • the coefficient of variation of particle size of the particles M is preferably not greater than 20%, more preferably not greater than 10%, and even more preferably not greater than 5%.
  • the pitch of the convex protrusions provided on the mold substrate 11 is equal to the modal pitch between the particles M. If the divergence D (%) of the arrangement is low, the pitch of the convex protrusions will be substantially the same as the average particle size A of the particles M. As such, the average particle size A of the particles M is appropriately selected so that convex protrusions with a desired pitch can be formed with high precision.
  • the particles M can be easily arranged in the particle arrangement step so that the divergence D is not greater than 10%. That is, an etching mask constituted by a monolayer of close-packed particles M can be disposed on the mold substrate 11 with extremely high precision.
  • the a particle monolayer F formed in the manner described above functions as a single particle etching mask 12.
  • the mold substrate 11, for which the single particle etching mask 12 is provided on one surface, is subjected to surface processing by gas-phase etching (etching step) so as to form convex protrusions on one surface of the mold substrate 11.
  • gas-phase etching etching step
  • etching gas passes through the gaps between the particles M that constitute the etching mask 12 and reaches the surface of the mold substrate 11, so that grooves are formed in that portion, and round pillars 13 appear at the respective positions corresponding to the particles M.
  • the particles M on the round pillars 13 are gradually etched and become small.
  • the convex protrusions can be formed.
  • the convex protrusions can be formed in a step shape ( FIG. 6C ).
  • the particles M constituting the a particle monolayer etching mask 12 are not particularly limited, and examples thereof include gold particles, colloidal silica particles, and the like.
  • a commonly used etching gas may be used. Examples thereof include Ar, SF 6 , F 2 , CF 4 , C 4 F 8 , C 5 F 8 , C 2 F 6 , C 3 F 6 , C 4 F 6 , CHF 3 , CH 2 F 2 , CH 3 F, C 3 F 8 , Cl 2 , CCl 4 , SiCl 4 , BCl 2 , BCl 3 , BC 2 , Br 2 , Br 3 , HBr, CBrF 3 , HCl, CH 4 , NH 3 , O 2 , H 2 , N 2 , CO, CO 2 , and the like.
  • the particles M and the etching gas may be changed in accordance with the mold substrate 11 to be etched.
  • the mold substrate 11 For example, in the case of a combination in which gold particles are selected as the particles constituting the a particle monolayer etching mask and a glass substrate is selected as the mold substrate, if an etching gas that reacts with glass such as CF 4 , CHF 3 , or the like is used, the etching rate of the gold particles will be relatively slower and the glass substrate will be selectively etched.
  • the comparatively soft PET substrate can be selectively physically etched by using an inert gas such as Ar or the like as the etching gas.
  • the convex protrusions of the mold substrate can be formed in a step shape ( FIG. 6C ).
  • the etching rate can be changed and the convex protrusions can be formed by selecting Si as the mold substrate 11, performing etching with a composition including Cl 2 and CF 4 at a composition ratio of 50:50 to 100:0, and during the etching, changing the etching gas to a composition including SF 6 and CH 2 F 2 at a composition ratio of 25:75 to 75:25.
  • Etching conditions include an antenna power of 1,500 W, a bias power of from 50 W to 300 W, and a gas flow rate of from 30 sccm to 50 sccm.
  • the positively charged particles in the etching gas that is in a plasma state accelerate and impact the substrate substantially vertically at a high speed.
  • a gas that reacts with the substrate, physico-chemical etching in the vertical direction occurs.
  • isotropic etching by the radicals produced by the plasma occurs in parallel.
  • the etching by the radicals is chemical etching, in which isotropic etching occurs in all directions of the etching subject.
  • the etching rate cannot be controlled by setting the bias power because radicals do not carry an electric charge, but the etching rate can be controlled by adjusting the concentration (flow rate) of the etching gas in the chamber.
  • the proportions of vertical etching and isotropic etching can be controlled by changing the concentration (flow rate) of the etching gas in the chamber and, as a result, the convex protrusions can be formed with a step shape.
  • the optical element in which the concave protrusions are formed in the anti-reflection layer 2 can be obtained by transferring from this mold (transfer an odd number of times).
  • the transferred product (the anti-reflection layer having the concave protrusions) is formed on a 1-for-1 basis with the mold and, as such, the pitch of the concave protrusions formed in the anti-reflection layer is equal to the pitch of the convex protrusions of the mold substrate 11, and displacements and the like in the arrangement of the concave protrusions formed in the anti-reflection layer match the mold.
  • the method for fabricating the mold is not limited to the method described above.
  • a photoresist mask in which a pattern is formed by interference exposure may be used instead of the a particle monolayer etching mask.
  • a mold having a corresponding convex shape can be fabricated.
  • the anti-reflection layer having concave protrusions can be fabricated by transferring from the mold an even number of times.
  • Examples of the transfer method described above include injection molding in which fluid material is poured into a mold and, thereafter, the surface shape of the mold surface is transferred by solidifying the material; so-called nanoimprinting in which the surface shape is transferred by pressing a mold into resin or a glass material; and the like.
  • the mold obtained through the method described above has any one of the following characteristics [1] to [3].
  • FIG. 12 is a drawing schematically illustrating a cross-section of the mold.
  • a mold 100 includes a substrate 101 and a plurality of convex protrusions c1' to cn'.
  • the mold 100 may include a flat portion f corresponding to the flat portion f in FIG. 1 .
  • the proportion of the convex protrusions that include the steps is determined as follows.
  • a cross-section along a line having a length of 5 ⁇ m in any direction and at any position such as that illustrated in FIG. 12 is obtained from an AFM image of the mold 100 or a microscope image obtained by actually cutting the mold.
  • the cross-section is a plane perpendicular to the arrangement plane on which the convex protrusions are arranged. In cases where the convex protrusions are systematically arranged, it is preferable that a direction along the arrangement direction of the convex protrusions is used as the cutting direction to obtain the cross-section.
  • any portion in which 30 to 40 or more convex protrusions are included in the cross-section is extracted, and the proportion of convex protrusions that include steps is calculated for the convex protrusions included in the extracted portion.
  • the diameter d m can be found as the maximum diameter of the convex protrusions observed in the cross-section perpendicular to the arrangement plane of the convex protrusions.
  • the procedure described for the definition of the width of the steps in the optical element 10 can be applied to the definition of the width w t of the steps in the mold 100.
  • the heights at which the steps are provided in the convex surface of the mold 100 are adjusted so that the concave protrusions of the optical element of the present invention have steps at the predetermined positions.
  • the depth at which the steps in the concave protrusion surface of the optical element are formed change depending on the transfer conditions and material.
  • transfer tests be performed using a plurality of prototype molds with different step positions and the mold and transfer conditions be optimized so that the optical element of the present invention can be manufactured with high accuracy.
  • the antireflective performance of the optical element of the present invention was confirmed by simulation. First, the simulation method will be described (refer to Applied Optics, Vol. 26, No. 6 1142-1146 (1987 ), Applied Optics, Vol. 32, No. 7 1154-1167 (1993 ), and the like).
  • Reflection when light enters an interface between a material with a refractive index of n o and a material with a refractive index of n s will be considered.
  • an article with the refractive index n s has a concave shape such as that illustrated in FIG. 8 .
  • the anti-reflection layer of the concave protrusions is sliced so as to divide it into N layers from the reference point side, so as to form a layered structure having a first layer to an Nth layer, in order from the reference point side.
  • the jth layer consists of repetitions of an air region with a width q and an anti-reflection layer region with a width 1-q.
  • the width here is the width of the interface with the j-1th layer.
  • the effective refractive index of the jth layer is n j
  • the thickness of this layer is d j .
  • n j can be found from the refractive indexes n o and n s , and the width q.
  • dj j can be found by dividing the modal depth of the concave protrusions by the number of layers N.
  • ⁇ j and ⁇ j are represented by Formula (10) and Formula (11) below.
  • ⁇ j 2 ⁇ / ⁇ n j d j cos ⁇ j
  • ⁇ j ⁇ n j cos ⁇ j s polarization n j / cos ⁇ j p polarization
  • the average reflectance was calculated while changing the total width w s of the steps and the average depth z s of the steps.
  • the depth h of the concave protrusions was 295 nm (average)
  • the modal pitch P was 120 nm
  • the diameter d was 120 nm (average).
  • the average reflectance was calculated as follows. First, the reflectance of the light that has entered the interface when projecting light of a wavelength of 380 nm at an angle of incidence of 5° was calculated using Formula (13). Then, the reflectance of light that has entered the interface for of every 20 nm up to a wavelength of 780 nm was calculated. The average of the reflectance of the light wavelengths was calculated and recorded as the average reflectance.
  • Example 2 Using concave protrusions that include two steps, as in Example 1, the average reflectance was calculated while changing the total width w s of the steps and the average depth z s of the steps.
  • the lateral width of each of the steps was w s /4 and the vertical width was 0.1h/2.
  • Table 2 The results are shown in Table 2.
  • the calculation conditions of the depth, modal pitch, diameter, and reflectance of the concave protrusions were the same as in Example 1.
  • Example 2 Using concave protrusions that include three steps, as in Example 1, the average reflectance was calculated while changing the total width w s of the steps and the average depth z s of the steps.
  • the lateral width of each of the steps was w s /6 and the vertical width was 0.1h/3. The results are shown in Table 3.
  • Example 2 the calculation conditions of the depth, modal pitch, diameter, and reflectance of the concave protrusions were the same as in Example 1.
  • the average reflectance at the same w s and z s in Table 2 and Table 3 are compared. It is clear that, in the regions surrounded by the dot-dash lines in Table 2 and Table 3, the average reflectance of Table 2 are lower than the average reflectance of Table 3. That is, in this range, the average reflectance is lower for cases with two steps (Table 2) than for cases with three steps (Table 3).
  • the number of steps can be set to be two or fewer.
  • the average reflectance was calculated while changing the shape of the envelope of the concave protrusions.
  • the shape of the concave protrusions was changed by changing the depth of the concave protrusions and width d 3/4 of the concave protrusions at a depth of 3/4h from the reference plane including the reference point.
  • the concave protrusions were provided with one step, the total width w s of the steps was fixed at 0.14d, and the average depth position z s of the steps was fixed at 0.48h. Additionally, the modal pitch P of the concave protrusions was 90 nm and the diameter d was 90 nm (average). Light entered an interface with a refractive index of 1.5 from air with a refractive index of 1.0, at an angle of incidence of 5°, and the refractive index of the material of the anti-reflection layer was also 1.5. The results are shown in Table 4. The rows in Table 4 are proportions of the width d 3/4 of the concave protrusions at a depth of 3/4h from the reference plane including the reference point, with respect to the diameter d of the concave protrusions.
  • Example 5 Other than setting the modal pitch of the concave protrusions to 120 nm and the diameter to 120 nm (average), the average reflectance was calculated in the same manner as in Example 4. The results are shown in Table 5. The rows in Table 5 are proportions of the width d 3/4 of the concave protrusions at a depth of 3/4h from the reference plane, with respect to the diameter d of the concave protrusions.
  • Example 6 Other than setting the modal pitch of the concave protrusions to 200 nm and the diameter to 200 nm (average), the average reflectance was calculated in the same manner as in Example 4. The results are shown in Table 6. The rows in Table 6 are proportions of the width d 3/4 of the concave protrusions at a depth of 3/4h from the reference plane, with respect to the diameter d of the concave protrusions.
  • the range surrounded by the dot-dash lines indicate average reflectance that are half or less than the average reflectance of a case where there are no steps (0.1047). These cases have high antireflective performance.
  • the shape of the envelope when the average reflectance is in this range is understood to be conical from the relationship between the depth of the concave protrusions and the width d 3/4 of the concave protrusions at a depth of 3/4h from the reference plane.
  • the concave protrusions were provided with one step, the total width w s of the steps was fixed at 0.14d, and the average depth z s of the steps was fixed at 0.48h. Additionally, the modal pitch P of the concave protrusions was 120 nm and the diameter d was 120 nm. Light entered an interface with a refractive index of 1.5 from air with a refractive index of 1.0, at an angle of incidence of 5°, and the refractive index of the material of the anti-reflection layer was also 1.5.
  • results for entrance of wavelengths in the visible light region are shown in Table 9
  • results for entrance of light of a wavelength in the near infrared region are shown in Table 10
  • results for entrance of light of a wavelength in the near ultraviolet region are shown in Table 11.
  • change in the average reflectance of the concave protrusions was calculated for cases where the modal depth of the concave protrusions was 245 nm, 295 nm, and 345 nm.
  • change in the average reflectance of the concave protrusions was also calculated for a case where there were no steps and the modal depth of the concave protrusions was 245 nm, 295 nm, and 345 nm. From this comparison, it is clear that particularly high antireflective performance is displayed when the modal depth is from 45% to 55% of the median of the wavelength range of the incident light. Specifically, extremely high antireflective performance is displayed when the modal depth of the concave protrusions is 295 nm with respect to visible light of 380 nm to 780 nm.

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EP3182178B1 (de) 2020-01-01

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